The present invention relates to a novel, disc-like, sulfur-containing compound usable as functional materials such as light-emitting device materials, discotic liquid crystal materials, organic conductive materials (electrically conductive charge-transporting complexes, electrically conductive radical salts, etc.), organic ferromagnetic materials, etc., and a light-emitting device using the compound.
Organic conductive materials have been researched and developed actively in recent years because they are light in weight and excellent in corrosion resistance, etc. unlike metal materials such as gold, silver and copper, and electrically conductive metal oxide materials such as ITO. Known as high-conductive, organic materials are most of charge-transporting complexes and radical cation salts, which are derived from electron-donating compounds having a 1,3-dithiol ring with a typical example of tetrathiafulvalene (TTF), and various electron-accepting compounds or inorganic anions.
It is known that discotic liquid crystals can be used as charge-transporting materials in various devices. For example, Adam, et al. reported that triphenylene-based, discotic liquid crystalline phase exhibited mobility of 10xe2x88x923 to 10xe2x88x922 cm2/Vs (Nature, Vol. 371, Page 141). Also disclosed are examples of using the discotic liquid crystals for such devices as organic electroluminescence (EL) devices.
Organic ferromagnetic materials have been actively researched for use in place of metal magnets such as iron-based magnets, etc. Reported by Breslow, R. is that in a charge-transporting complex derived from a dication of donor molecule and a dianion of acceptor molecule, one molecule is stably in a triplet ground state with parallel spins to provide ferromagnetic interaction (Pure and Applied Chemistry, Vol. 54, page 927, 1982). According to the group theory, a molecule with symmetry of C3 or more or D2d has a degenerate molecular orbital and can be converted into the triplet ground state. Therefore, various high-symmetry molecules have been developed to synthesize ferromagnetic substances.
However, the organic conductive materials, the charge-transporting liquid crystals and the organic ferromagnetic materials mentioned above fail to show sufficient performance for industrial use.
Research and development are recently active worldwide to provide various light-emitting devices. Among others, organic electroluminescence (EL) devices are advantageous in that they are extremely thin, light in weight, rapid in response, wide in viewing angle, low in driving voltage, etc., thereby attracting much attention as a promising light-emitting device. Although various materials have been evaluated as components for the light-emitting devices to develop highly efficient devices with external quantum efficiency of more than 10%, they are still insufficient in durability and need a high driving voltage.
JP 11-111462 A discloses a light-emitting device comprising a compound with a dithiol ring, but it is different in structure from the compound of the present invention.
Accordingly, an object of the present invention is to provide a novel, disc-like, sulfur-containing compound having charge transportability and electron-donating properties.
Another object of the present invention is to provide a light-emitting device excellent in durability, which can be driven at a low driving voltage.
The compound according to the present invention has a chemical structure represented by the general formula (I): 
wherein each of R1 to R12 and RA1 to RA6 represents a hydrogen atom or a substituent group, and adjacent groups of R1 to R12 and RA1 to RA6 may be bonded to each other to form a ring.
The compound of the present invention is preferably has a chemical structure represented by the general formula (II): 
wherein each of R1 to R12 and RB1 to RB12 represents a hydrogen atom or a substituent group.
The light-emitting device according to the present invention comprises a pair of electrodes and one or more organic layers comprising a light-emitting layer disposed therebetween, at least one of the organic layers comprising at least one compound represented by the general formula (I) or (II).
In the light-emitting device of the present invention, at least one of the organic layers is preferably a layer having at least one compound represented by the general formula (I) or (II) dispersed in a polymer.
Each of R1, R4, R5, R8, R9 and R12 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. Each of R2, R3, R6, R7, R10 and R11 is preferably a hydrogen atom, an alkyl group, an alkylthio group, an alkyloxy group, a cyano group, alkyloxy group or a halogen atom, more preferably a hydrogen atom, an alkyl group or an alkylthio group. Each of RA1 to RA6 is preferably a hydrogen atom, alkyl group, alkyloxy group, alkylthio group, a cyano group or halogen atoms, more preferably a hydrogen atom, alkyl group or alkylthio group. Each of RB1 to RB12 is preferably a hydrogen atom or an alkyl group.
At least one organic layer in the light-emitting device preferably further comprises a polymer. The above at least one organic layer is preferably a hole-injecting layer or a hole-transporting layer.
The amount of the compound represented by the formula (I) or (II) in a hole-injecting layer or a hole-transporting layer is preferably from 10 to 100% by weight, more preferably from 50 to 100% by weight. The amount of the compound represented by the formula (I) or (II) in the other layers except a hole-injecting layer or a hole-transporting layer is preferably from 5 to 90% by weight, more preferably from 5 to 50% by weight.
[1] Sulfur-containing Compound
In the general formula (I), each of R1 to R12 and RA1 to RA6 represents a hydrogen atom or a substituent group, and may be the same or different. Examples of the substituent groups represented by R1 to R12 and RA1 to RA6 include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, an amino group, acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkylsulfonylamino groups, arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, a sulfo group, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, a carbamoyl group, arylazo groups, heterocyclic azo groups, imide groups, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group and silyl groups. The adjacent groups of R1 to R12 and RA1 to RA6 may be bonded to each other to form a ring, if possible.
Each of R1, R4, R5, R8, R9 and R12 is preferably a hydrogen atom or an alkyl group and particularly a hydrogen atom. The above alkyl group is a group preferably with 1 to 3 carbon atoms, more preferably with 1 or 2 carbon atoms, particularly a methyl group.
In a case where the compound represented by the general formula (I) is used as a liquid crystal material, preferred examples of R2, R3, R6, R7, R10 and R11 include alkyl groups, the number of carbon atoms thereof being preferably 2 to 30, more preferably 2 to 20, which may be unsubstituted alkyl groups such as an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and an eicosyl group; or substituted alkyl groups such as a 4-methoxybutyl group and a 6-methoxyhexyl group; alkyloxy groups, the number of carbon atoms thereof being preferably 2 to 30, more preferably 2 to 20, which may be unsubstituted alkyloxy groups such as an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, an undecyloxy group and a dodecyloxy group; or substituted alkyloxy groups such as a 4-methoxybutyloxy group and a 6-methoxyhexyloxy group; acyloxy groups, the number of carbon atoms thereof being preferably 3 to 30, more preferably 3 to 20, which may be unsubstituted acyloxy groups such as an acetoxy group, a propionyloxy group, a butyryloxy group, a valeryloxy group, a hexanoyloxy group, a heptanoyloxy group, an octanoyloxy group, a nonanoyloxy group, an undecanoyloxy group and a dodecanoyloxy group; or substituted acyloxy groups such as a 4-methoxybutyryloxy group and a 6-methoxyhexanoyloxy group; alkoxycarbonyl groups, the number of carbon atoms thereof being preferably 3 to 30, more preferably 3 to 20, which may be unsubstituted alkoxycarbonyl groups such as an ethoxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a nonyloxycarbonyl group, an undecyloxycarbonyl group and a dodecyloxycarbonyl group; or substituted alkoxycarbonyl groups such as a 4-methoxybutyloxycarbonyl group and a 6-methoxyhexyloxycarbonyl group; benzoyloxy groups; and cinnamoyloxy groups. Each of the benzoyloxy groups and the cinnamoyloxy groups may have, at a para position, a substituent group such as an alkyloxy group, an alkyl group, an alkoxycarbonyl group, an acyloxy group, a halogen atom, etc, preferably an alkyloxy group, which may be the same as the above-mentioned alkyloxy group of R2, R3, R6, R7, R10 and R11. Each of R2, R3, R6, R7, R10 and R11 is more preferably an alkyl group or an alkyloxy group, most preferably an alkyloxy group.
In a case where the compound represented by the general formula (I) is used for other applications than the liquid crystal material, preferred examples of R2, R3, R6, R7, R10 and R11 include a hydrogen atom; alkyl groups, the number of carbon atoms thereof being preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly 1 to 5, such as a methyl group, an ethyl group and a propyl group; alkoxy groups, the number of carbon atoms thereof being preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly 1 to 5, such as a methoxy group, an ethoxy group and an ethylenedioxy group formed by R2 and R3, R6 and R7, or R10 and R11; alkylthio groups, the number of carbon atoms thereof being preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly 1 to 5, such as a methylthio group, an ethylthio group, and a methylenedithio group, an ethylenedithio group and a propylenedithio group formed by R2 and R3, R6 and R7, or R10 and R11; aryl groups, the number of carbon atoms thereof being preferably 6 to 30, more preferably 6 to 20, further preferably 6 to 10, such as a phenyl group, a naphthyl group and an azulenyl group; heterocyclic groups, the number of carbon atoms thereof being preferably 2 to 30, more preferably 3 to 20, further preferably 3 to 10, which may have such a heterocycle as a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, a tellurophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, an oxazole ring, a thiazole ring, an isoxazole ring, an isothiazole ring, an imidazole ring, a triazine ring, a pyrane ring, a piperazine ring, a pyrroline ring, a pyrrolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazoline ring, a pyrazolidine ring, a furazan ring, a morpholine ring, an indole ring, an indoline ring, an indazole ring, a chromene ring, a chroman ring, an isochroman ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a phthalazine ring, a quinazoline ring, a quinoxaline ring, a naphthyridine ring, a purine ring, a pteridine ring, an indolizine ring, a carbazole ring, an acridine ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a xanthene ring, a phenoxazine ring, a thianthrene ring and a quinuclidine ring, the heterocycle being preferably a thiophene ring, a furan ring, a pyrrole ring or a pyridine ring, more preferably a thiophene ring or a pyridine ring, particularly a thiophene ring; a cyano group; a mercapto group; a hydroxyl group; and halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Each of R2, R3, R6, R7, R10 and R11 is more preferably a hydrogen atom, an alkyl group, an alkylthio group, an alkyloxy group, a cyano group or a halogen atom, further preferably a hydrogen atom, an alkyl group, an alkylthio group or a halogen atom, most preferably a hydrogen atom, an alkyl group or an alkylthio group, particularly a hydrogen atom.
Preferred examples of RA1 to RA6 include a hydrogen atom; a benzene ring formed by RA1 and RA2, RA3 and RA4, or RA5 and RA6 with a dithiol ring; alkyl groups, the number of carbon atoms thereof being preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly 1 to 5, such as a methyl group, an ethyl group and a propyl group; alkoxy groups, the number of carbon atoms thereof being preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly 1 to 5, such as a methoxy group, an ethoxy group and an ethylenedioxy group formed by RA1 and RA2, RA3 and RA4, or RA5 and RA6; alkylthio groups, the number of carbon atoms thereof being preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 10, particularly 1 to 5, such as a methylthio group, an ethylthio group, and a methylenedithio group, an ethylenedithio group and a propylenedithio group formed by RA1 and RA2, RA3 and RA4, or RA5 and RA6; aryl groups, the number of carbon atoms thereof being preferably 6 to 30, more preferably 6 to 20, further preferably 6 to 10, such as a phenyl group and a naphthyl group; heterocyclic groups, the number of carbon atoms thereof being preferably 2 to 30, more preferably 3 to 20, further preferably 3 to 10, which may have such a heterocycle as a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, a tellurophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, an oxazole ring, a thiazole ring, an isoxazole ring, an isothiazole ring, an imidazole ring, a triazine ring, a pyrane ring, a piperazine ring, a pyrroline ring, a pyrrolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazoline ring, a pyrazolidine ring, a furazan ring, a morpholine ring, an indole ring, an indoline ring, an indazole ring, a chromene ring, a chroman ring, an isochroman ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a phthalazine ring, a quinazoline ring, a quinoxaline ring, a naphthyridine ring, a purine ring, a pteridine ring, an indolizine ring, a carbazole ring, an acridine ring, a phenazine ring, a phenanthridine ring, a phenanthroline ring, a xanthene ring, a phenoxazine ring, a thianthrene ring and a quinuclidine ring, the heterocycle being preferably a thiophene ring, a furan ring, a pyrrole ring or a pyridine ring, more preferably a thiophene ring or a pyridine ring, particularly a thiophene ring; a cyano group; a mercapto group; a hydroxyl group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a carboxyl group; and carbonyloxy groups, the number of carbon atoms thereof being preferably 2 to 30, more preferably 2 to 20, further preferably 2 to 10, such as a methoxycarbonyl group and an ethoxycarbonyl group. More preferred among them are a hydrogen atom, a benzene ring formed by RA1 and RA2 and RA4, or RA5 and RA6, alkyl groups, alkyloxy groups, alkylthio groups, a cyano group and halogen atoms. Furthermore preferred are a hydrogen atom, a benzene ring formed by RA1 and RA2 RA3 and RA4, or RA5 and RA6, alkyl groups and alkylthio groups.
Each of R1 to R12 and RA1 to RA6 may further have a substituent group, and examples thereof may be the same as those of R1 to R12 and RA1 to RA6. Each of R1 to R12 and RA1 to RA6 may have a ring structure, which may be condensed.
A preferred example of the compound of the present invention represented by the general formula (I) is represented by the general formula (II). 
R1 to R12 in the general formula (II) are the same as those in the general formula (I). Each of RB1 to RB12 represents a hydrogen atom or a substituent group, with examples the same as those of R1 to R12 and RA1 to RA6. Each of RB1 to RB12 is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom.
Specific examples of the compound of the present invention represented by the general formula (I) or (II) will be illustrated below without intention of restriction. 
[2] Method for Synthesizing Sulfur-containing Compound
Though not particularly limited, the compound of the present invention represented by the general formula (I) or (II) is preferably synthesized by a coupling reaction between a truxene compound and a compound having a 1,3-dithiol ring skeleton because of easiness.
Preferred as the truxene compound is, for example, 1H-tribenzo[a,f,k]trindene-5,10-dihydro-5,10,15-trione having three carbonyl groups (truxenequinone). The truxene compound can be easily synthesized by such a method as self-condensation of indandione using a base (K. Jacob, et al., European Journal of Organic Chemistry, 2000, pp. 2047 to 2055), self-condensation of indandione using an acid (F. Sbrogio, et al, Synlett, 1994, pp. 761 to 762), etc. The temperature and time of the self-condensation reactions are not particularly limited and may be controlled according to the above references. The base may be added in amount of 1 to 2 equivalent to indandione, and the acid may be added in amount of 1 equivalent to large excess to indandione.
Preferred as the compound having a 1,3-dithiol ring skeleton are carbanions derived from phosphonium compounds represented by the general formula (III), carbanions derived from phosphonate compounds represented by the general formula (IV), and equivalents thereof. R31 and R32 in the general formula (III) and R41 and R42 in the general formula (IV) are the same as RA1 to RA6 in the general formula (I). Each of R33 in the general formula (III) and R43 in the general formula (IV) is not particularly limited but preferably an aryl group or an alkyl group having 1 to 20 carbon atoms, more preferably a phenyl group, a methyl group, an ethyl group or a butyl group. 
The carbanion or equivalent thereof derived from the compound of the general formula (III) or (IV) is subjected to the coupling reaction with the ketone. The coupling reaction is well known and disclosed in Ishikawa, Akiba and Inamoto, Tetrahedron Letters, 1976, No. 41, pp. 3695 to 3698, etc. For example, the carbanion may be prepared by the steps of dissolving the phosphonate compound of the general formula (IV) in tetrahydrofuran, cooling the resultant solution to xe2x88x9270xc2x0 C. or lower, and adding an n-butyl lithium hexane solution to the cooled solution dropwise.
Truxenequinone in a state of solid or solution of tetrahydrofuran, etc. may be added to the carbanion solution and gradually heated to room temperature. The resultant mixture may be extracted with chloroform, etc. and purified by recrystallization, to obtain the compound of the present invention represented by the general formula (I) or (II) with a high purity.
[3] Light-emitting Device
The production method of the organic layer in a light-emitting device comprising the compound of the present invention is not particularly limited, and may be selected from a resistance-heating vapor deposition method, an electron beam method, a sputtering method, a molecular-stacking method, a coating method, an inkjet-printing method, a printing method, a transferring method, an electrophotography method, etc. Preferred among them are a resistance-heating vapor deposition method and a coating method because of good properties of the resultant light-emitting device and simplicity in process.
When the compound of the present invention is used as a light-emitting material, it may be used in any of a hole-injecting layer, a hole-transporting layer, an electron-injecting layer, an electron-transporting layer, a light-emitting layer, a hole-blocking layer and an electron-blocking layer, though it is preferably used in a hole-injecting layer or a hole-transporting layer.
In the case of using the compound of the present invention in a hole-injecting layer or a hole-transporting layer, the amount of the compound is preferably 10 to 100% by weight, more preferably 50 to 100% by weight, most preferably 80 to 100% by weight, particularly 100% by weight, based on the total weight of the layer comprising the compound. In the case of using the compound in the other layers, amount of the compound is preferably 5 to 90% by weight, more preferably 5 to 50% by weight, most preferably 5 to 30% by weight, based on the total weight of the layer comprising the compound. In any case, the compound of the present invention is uniformly dispersed in a polymer when these layers contain a polymer described below.
The light-emitting device of the present invention comprises a light-emitting layer or a plurality of organic layers including the light-emitting layer between a pair of electrodes, a positive electrode and a negative electrode. The light-emitting device of the present invention may comprise a hole-injecting layer, a hole-transporting layer, an electron-injecting layer, an electron-transporting layer, a hole-blocking layer, an electron-blocking layer, a protective layer, etc. in addition to the light-emitting layer. These layers may have other functions than their inherent functions.
(A) Electrodes
The positive electrode acts to supply holes to the hole-injecting layer, the hole-transporting layer, the light-emitting layer, etc. The positive electrode may be made of a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, etc., and is preferably made of a material having a work function of 4.0 eV or more. Examples of the material for the positive electrode include electrically conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO); metals such as gold, silver, chromium and nickel; mixtures and laminates of the electrically conductive metal oxides and the metals; electrically conductive inorganic compounds such as copper iodide and copper sulfide; electrically conductive organic compounds such as polyaniline, polythiophene and polypyrrole; mixtures and laminates of the electrically conductive organic compounds and ITO; etc. Preferable among them are the electrically conductive metal oxides, particularly ITO from the viewpoints of productivity, electroconductivity, transparency, etc.
Although the thickness of the positive electrode may be appropriately determined depending on the material used therefor, it is preferably 10 nm to 5 xcexcm, more preferably 50 nm to 1 xcexcm, further preferably 100 nm to 500 nm.
The positive electrode is generally formed on a substrate made of a soda lime glass, a non-alkali glass, a transparent resin, etc. The glass substrate is preferably made of a non-alkali glass to reduce ion elution. In the case of using the soda lime glass, a barrier coating of silica, etc. is preferably formed thereon beforehand. The thickness of the substrate is not particularly limited as long as it has sufficient mechanical strength. In the case of the glass substrate, the thickness thereof is generally 0.2 mm or more, preferably 0.7 mm or more.
A method for forming the positive electrode may be selected depending on the material used therefor. For example, the positive electrode made of ITO may be formed by an electron beam method, a sputtering method, a resistance-heating vapor deposition method, an ion plating method, a chemical reaction method such as a sol-gel method, a spraying method, a dipping method, a thermal CVD method, a plasma CVD method, a coating method using an ITO dispersion, etc.
To lower the driving voltage or to increase the light-emitting efficiency of the light-emitting device, the positive electrode may be subjected to a washing treatment, etc. For example, a UV-ozone treatment and a plasma treatment are effective in the case of the positive electrode of ITO.
The negative electrode acts to supply electrons to the electron-injecting layer, the electron-transporting layer, the light-emitting layer, etc. The material for the negative electrode may be selected from metals, alloys, metal oxides, electrically conductive compounds, mixtures thereof, etc. depending on ionization potential, stability, adhesion to a layer adjacent to the negative electrode such as the light-emitting layer. Examples of materials for the negative electrode include alkali metals such as Li, Na, K and Cs, and fluorides thereof; alkaline earth metals such as Mg and Ca, and fluorides thereof; gold; silver; lead; aluminum; alloys and mixtures of sodium and potassium; alloys and mixtures of lithium and aluminum; alloys and mixtures of magnesium and silver; rare earth metals such as indium and ytterbium; mixtures thereof; etc. The negative electrode is preferably made of a material having a work function of 4.0 eV or less, more preferably made of aluminum, an alloy or a mixture of lithium and aluminum, or an alloy or a mixture of magnesium and silver. In the mixtures of two metals such as lithium and aluminum, the component metals are mixed with each other without forming an alloy.
Although the thickness of the negative electrode may be appropriately determined depending on the material used therefor, it is preferably 10 nm to 5 xcexcm, more preferably 50 nm to 1 xcexcm, further preferably 100 nm to 1 xcexcm.
The negative electrode may be formed by an electron beam method, a sputtering method, a resistance-heating vapor deposition method, a coating method, etc. A negative metal electrode may be formed by a metal deposition method, and a negative alloy electrode may be formed by simultaneously deposition of a plurality of metals or by deposition of an alloy.
The positive electrode and the negative electrode preferably have as low a sheet resistance as possible. Their sheet resistance is preferably a few hundred xcexa9/square or less.
(B) Light-emitting Layer
The light-emitting material for the light-emitting layer is not particularly limited as long as it has functions of receiving holes provided from the positive electrode, the hole-injecting layer, the hole-transporting layer, etc.; receiving electrons provided from the negative electrode, the electron-injecting layer, the electron-transporting layer, etc.; transporting charges; and emitting light by recombining holes and electrons when an electric field is applied to the light-emitting device. Examples of the light-emitting material include benzoxazole; benzoimidazole; benzothiazole; styrylbenzene; polyphenyl; diphenylbutadiene; tetraphenylbutadiene; naphthalimido; coumarin; perylene; perynone; oxadiazole; aldazine; pyralidine; cyclopentadiene; bis(styryl)anthracene; quinacridon; pyrrolopyridine; thiadiazolopyridine; styrylamine; aromatic dimethylidine compounds; 8-quinolinol derivative metal complexes; phenylpyridine derivative metal complexes; metal complexes such as organometallic complexes and rare-earth metal complexes; polymers such as polythiophene, polyphenylene and polyphenylenevinylene; the compound of the present invention; derivatives thereof; etc.
Though not particularly limited, the thickness of the light-emitting layer is preferably 1 nm to 5 xcexcm, more preferably 5 nm to 1 xcexcm, further preferably 10 nm to 500 nm.
Though not particularly limited, the light-emitting layer may be formed by a resistance-heating vapor deposition method; an electron beam method; a sputtering method; a molecular-stacking method; a coating method such as a spin-coating method, a casting method and a dip-coating method; an LB method; an ink-jet method; a printing method; a transferring method; an electrophotography method; etc. Preferable among them are the resistance-heating vapor deposition method and the coating method.
(C) Hole-injecting Layer and Hole-transporting Layer
The hole-injecting material and the hole-transporting material used for the hole-injecting layer and the hole-transporting layer are not particularly limited as long as they have a function of injecting holes provided from the positive electrode into the light-emitting layer, transporting holes, and/or blocking electrons provided from the negative electrode. Examples of the hole-injecting material and the hole-transporting material include the disc-like, sulfur-containing compounds of the present invention, carbazole, imidazole, triazole, oxazole, oxadiazole, polyarylalkanes, pyrazoline, pyrazolone, phenylenediamine, arylamines, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic tertiary amine compounds, styrylamine, aromatic dimethylidyne compounds, porphyrin compounds, polysilane compounds, poly(N-vinylcarbazole), aniline copolymers, electrically conductive polymers and oligomers such as oligothiophenes and polythiophenes, derivatives thereof, etc.
Although the thickness of each of the hole-injecting layer and the hole-transporting layer may be appropriately determined depending on the material used therefor, it is preferably 1 nm to 5 xcexcm, more preferably 5 nm to 1 xcexcm, further preferably 10 nm to 500 nm. Each of the hole-injecting layer and the hole-transporting layer may have a single-layer structure of one or more materials, or a multi-layer structure having a plurality of layers made of the same or different materials.
The hole-injecting layer and the hole-transporting layer may be formed by a vacuum deposition method; an LB method; an ink-jet method; a printing method; a transferring method; an electrophotography method; a coating method using a solution or dispersion containing the above material such as a spin-coating method, a casting method and a dip-coating method; etc. A resin may be added to a solution or a dispersion used in the coating method. Examples of the resins include poly(vinyl chloride), polycarbonates, polystyrene, poly(methyl methacrylate), polyesters, polysulfones, poly(phenylene oxide), polybutadiene, poly(N-vinylcarbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl celluloses, poly(vinyl acetate), ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, etc.
(D) Electron-injecting Layer and Electron-transporting Layer
The electron-injecting material and the electron-transporting material used for the electron-injecting layer and the electron-transporting layer are not particularly limited as long as they have a function of injecting electrons provided from the negative electrode into the light-emitting layer, transporting the electrons, and/or blocking holes provided from the positive electrode. Examples of the electron-injecting material and the electron-transporting material include triazole; triazine; oxazole; oxadiazole; fluorenone; anthraquinodimethane; anthrone; diphenylquinone; thiopyran dioxide; carbodimide; fluorenylidenemethane; distyrylpyrazine; anhydrides derived from a tetracarboxylic acid having such an aromatic ring as a naphthalene ring and a perylene ring; phthalocyanine; metal complexes such as 8-quinolinol derivative metal complexes, metallophthalocyanines and metal complexes containing a benzoxazole ligand or a benzothiazole ligand; the compound of the present invention; derivatives thereof; etc.
Though not particularly limited, the thickness of each of the electron-injecting layer and the electron-transporting layer is preferably 1 nm to 5 xcexcm, more preferably 5 nm to 1 xcexcm, further preferably 10 nm to 500 nm. Each of the electron-injecting layer and the electron-transporting layer may have a single-layer structure of one or more materials, or a multi-layer structure having a plurality of layers made of the same or different materials.
The electron-injecting layer and the electron-transporting layer may be formed by a vacuum deposition method; an LB method; an ink-jet method; a printing method; a transferring method; an electrophotography method; a coating method using a solution or a dispersion containing the above material such as a spin-coating method, a casting method and a dip-coating method; etc. The solution and the dispersion used in the coating method may comprise the same resin as in the hole-injecting layer and the hole-transporting layer.
(E) Protective Layer
The material used for the protective layer is not particularly limited as long as it has a function of shielding the light-emitting device from the penetration of moisture, oxygen, etc. that deteriorates the device. Examples of such materials include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti and Ni; metal oxides such as MgO, SiO, SiO2, Al2O3, GeO, NiO, CaO, BaO, Fe2O3, Y2O3 and TiO2; metal fluorides such as MgF2, LiF, AlF3 and CaF2; polyethylene; polypropylene; polymethyl methacrylate; polyimides; polyureas; polytetrafluoroethylene; polychlorotrifluoroethylene; polydichlorodifluoroethylene; copolymers of chlorotrifluoroethylene and dichlorodifluoroethylene; copolymers of tetrafluoroethylene and at least one comonomer; fluorine-containing copolymers having main chains with cyclic structures; moisture-absorbing materials having a water absorption of 1% or more; moisture-resistant materials having a water absorption of 0.1% or less; etc.
Though not particularly limited, the protective layer may be formed by a vacuum deposition method, a sputtering method, an activated sputtering method, a molecular beam epitaxy method (MBE method), a cluster ion beam method, an ion-plating method, a plasma polymerization method, a high-frequency excitation ion-plating method, a plasma CVD method, a laser CVD method, a thermal CVD method, a gas source CVD method, a coating method, an ink-jet method, a printing method, a transferring method, an electrophotography method, etc.
The present invention will be described in more detail below with reference to Examples without intention of restricting the scope of the present invention.